Vinylethinyl derivatives and processes for preparing same



* Patented June 19, 1934 TENT. mac

.VINYLETHINYL DERIVATIVES am) moo- ESSES FOR PREPARING SAME Wallace n.Cal-others, Fairville, 1a., J. Berchet, Wilmington, du Pont-de Nemours &

Del.,

No Drawing.

Application November Serial No. 574,456

and Gerard Del., assignors to E. I. Company, Wilmington,

a corporation of Delaware 32 Claims. 01. 266-112 This invention relatesto certain new and useful org'ano-metallic compounds and materialsderived therefrom, and to the method of preparing the same. Theinvention pertains particu-,

- larly to vinylethinyi magnesium compounds and to new and usefulproducts obtained therefrom.

Monovinylacetylene,

cuppa- 05 011, was first prepared by Willstatter and-Wirth (Ber.

46', 535) who, however, obtained it only in very small amounts andreported no study of its chemical behavior. More recently, an improvedprocess of preparation has been discovered by J. A.

Nieuwland, U. S. application Serial lflo. 305,866, filed September 13,1928, U. S. Patent No. 1,811,959.

Monovinylacetylene is ahi'ghly unsaturated compound and it shows anextraordinary tendency to undergo reactions of addition andpolymerization. We have discovered that it is possible, nevertheless, toconvert monovinylacetylene into derivatives in which the acetylenichydrogen atom has been replaced by magnesium. These are new compoundsand they can be used to prepare a great number of derivatives containingthe vinylethinyl group.

An object of the present invention relates to magnesium derivatives ofmonovinylacetylene and their mode of preparation. A further object ofthe invention comprehends numerous novel prod: ucts which may beobtained from the magnesium derivatives of monovinylacetylene, and theprocesses utilized in preparingsuch new products. One method of thepresent invention consists in treating monovinylacetylene,

aspen-Ceca,

with an organo-magnesium compound derived from an alkyl or an arylhalide and metallic magnesiuml Solutions containing such;organomagnesium compounds (Grignard reagents) are readily prepared bythe well-known method of amine. 1 7

treating an alkyl or aryl halide with metallic magnesium in the presenceof a suitable solvent such as an'ether or a tertiary airline, or ahydro- "carbon solvent containing an ether or a tertiary are usuallyrepresented by the formula RMgX in which R v is a hydrocarbon radicaland Xis a halogen atom although it is recognized (cf Noller,

J. Am. Chem. Soc., 53, 635 (1931)) that they may have the formula RzMg,or that they may be in equilibrium with compounds of the formula RzMg.

It is recognized also that such reagents usually exist in solution in astate of chemical combination with the (ether) solvent, but thiscombined ether does not participate in the reactions of the Grignardreagents. 1 According to the process of the present inven-' tion webring together with monovinylacetylene a solution such as an etherealsolution of a Grignard reagent, whereupon a' vigorous reaction takesplace in accordance with the following equation:

The reagent RMgX (RzMg) is destroyed, the alkyl or aryl radical R beingconverted into the corresponding hydrocarbon RH which, according to itsboiling point, may be evolved as a gas or may remain in solution, andthere results a solution which contains as its active ingredient avinylethinyl magnesium derivative. This derivative may be considered ascorresponding to the formula CH2=CHC ,CMgY in which Y represents ahalogen atom or a vinylethinyl group. This solution may be usedimmediately to react with a compound such as an aldehyde or a ketoneinto which it is desired to introduce the vinyl-" ethinyl group, or itmaybe stored for subsequent use. The vinylethinyl magnesium derivativesare. rapidly decomposed with the regeneration of monovinylac'etylene bythe action of water, alcohols, acids, and' other substances that containrea'ctive hydrogen, and they are also acted on more slowly by oxygen,air, and by carbon dioxide. Their solutions are preferably stored in Qcompletely filled, tightly closed containers in a cool, dark place.Under these conditions they can be kept for a long period of timewithout significant deterioration. For the purpose of using the,vinylethinyl magnesium compounds'as reagents to effect chemicaltransformations it is not necessary, and in general itis not desirableto attempt to separate or isolate them from the solutions'in which theyare formed. In preparing vinylethinyl magnesium com- 10 pounds accordingtofithe method of the present invention'we may use as the reactant anorganemagnesium compound (Grignard reagent) prepared frompany alkyl' orand halide "and metallic magnesium- Thus, we may prepare the reagent bytreating metallic magnesium with methyl chloride, methyl bromide, methyliodide, ethyl chloride, bromide, or iodide, phenyl chloride, bromide oriodide, etc. For small scale preparations {methyl bromide or ethylbromide is a preferred is a gas (B. P. 6 C.).

' a refrigerated container.

halideon account of the ease with which it is handled; for large scalepreparations methyl chloride or ethyl chloride is preferred because ofits cheapness. 7

In accordance with .the present invention such a Grignard reagent ismixed with monovinylacetylene so as to bring about a reaction resultingin the formation of the vinylethinyl magnesium compound. This mixing maybe brought about in any suitable manner, but it is necessary to takeinto account the fact that monovinylacetylene at ordinary temperaturesand pressures A preferred method of bringing about the mixing is tointroduce the gaseous monovinylacetylene in a fine stream under thesurface of the Grignard reagent which is contained in a cooled vesselprovided with a reflux condenser. It is desirable, though not necessary,to stir the reaction mixture during this process with the aid of amechanical stirrer.

been introduced (one mol for one mol of Grignard reagent) the mixturecan be heated for a short time so that it refluxes gently to insurecompletion of the reaction. Another method is to add themonovinylacetylene slowly in liquid form from The monovinylacetylene canalso be dissolved in a solvent such as ether or benzene. It is alsopossible to add a solu-. tion of the Grignard reagent to the liquid ordissolved.monovinylacetylene, but in general it is easier to avoidlosses if the monovinylacetylene is added to the Grignard reagent. It ispreferable in any event to use a slight excess of themonovinylacetyleneto insure complete utilization of the initial Grignardreagent. i

By way of illustration we present the following examples:

EXAMPLE I p Seventy-two grams of magnesium in the form of shavings'areplaced in a flask provided with a reflux condenser, a mechanical stirrerand (near the bottom) an inlet tube for gas. The magnesium' is coveredwith 1200 cc. of dry diethyl ether. The stirrer is started .and a fewdrops of methyl iodide are added to the mixture. As soon as themagnesium has been slightly etched by the action of the methyl iodide, aslow stream of methyl chloride is introduced thru the gas inlet tube.The magnesium gradually dissolves to form a solution of methyl magnesiumchloride. When all the magnesium has gone into solution, the gas inlettube is-disconnected from the methyl chloride tank and connected to avessel containing monovinylacetylene. The reaction flask is cooled withan ice bath and a stream'ofmonovinylacetylene is passed in through thegas inlet tube at such a rate that the ether refluxes only very slowly.'After 1'72 g. of monovinylacetylene have been introduced, the reactionis practically complete. .To insure complete reaction the solution .isgently heated to reflux for a short-time. The

solution now contains the equivalent of about 2.7 mols of vinylethinylmagnesium chloride.

EXAMPLE II After the calculated amount of monovinylacetylene has In thedropping" run slowly into the stirred solution. The reacton proceedssmoothly with the evolution of ethane, most of which escapes through thetop of the reflux condenser. After the addition of all themonovinylacetylene the mixture is gently heated for 30-45 minutes. Thereaction is then complete and the solution contains nearly thetheoretical amount of vinylethinyl magnesium bromide or its equivalent.This solution may be used directly as a reagent for the preparation ofother compounds containing the. vinylethinyl group, as is illustrated ina subsequent portion of the specification.

Thevinylethinyl magnesium compounds prepared by the method described inthis invention are new compounds. They react very. smoothly withanextraordinary variety of substances to produce derivatives containingthe vinylethinyl group, and they thus make readily accessible a greatmany types of compounds that have in the past been diiflcult orimpossible to prepare.

For the purpose of discussing the behavior of the vinylethinyl magnesiumcompounds we may represent them by the general formula and that ineither form they may be combined chemically to a greater or less extentwith the ether or other solvent in which .they are dissolved. Thevalidity of the following description of our invention however isnotdependent upon the question of the exact structure of these compoundswhich we shall for brevity refer to as vinylethinyl magnesium halidesand represented by the formula According to the present invention weproduce compounds containing the vinylethinyl group by acting onvinylethinyl magnesium halides with various types of reactants. Asreactants we may use any compounds containng the nuclei A=B or AEB inwhich A and B represent atoms of two different elements which aremutually united by more than one covalent bond. By a covalent bond wemean a pair of shared electrons. Sidgwick-The Electronic Theory ofValence, Oxford University Press, Oxford, 1927. Examples of suchreactants are aldehydes, RCH=O, such as formaldehyde, acetaldehyde,butyraldehyde, heptaldehyde, capraldehyde, stearaldehyde, acrole'in,crotonaldehyde; ketones, R2C=O, such as acetone, methylethyl ketone,acetophenone, benzophenone, stearone, methylene acetone. butyrone;carbon dioxide, O=C=O; esters, RC: 0(OR'), such as ethyl formate, ethylbutyrate.

methyl benzoate, butyl naphthoate, nitriles,-

This is discussed on page 83, et seq., of

thyl isocyanate; isothiocyanates, such as ethyl 'isothiocyanate, alkylisothiocyanate, etc. The nature of the action of the vinylethinylmagnesium-halide on these reactants cons sts in addition at the doubleor triple bond as illustrated by the following equations:

vided with a mechanical stirrer and a well cooled reflux condenser, andto add the reactant slowly or in small portions from a suitablecontainer. The reactant may be added as such or, as is especiallyconvenient in case the reactant is a solid,

7 it may be dissolved in a solvent suchas dry ether We may also use asreactants, very reactive .alkyl halides such as triphenyl chloromethane,benzyl' chloride, allyl bromide, etc., and estersjof sulfuric andsulfonic acids such as diethyl suliate, dime thyl sulfate, butyl p-to1uene .sulfonate and ethyl. benzene sulfonate. "The nature of the'action of the vinylethinyl magnesium halide on these) reactants isillustrated by the following equations:

or benzene. In certain cases it is better to add the vinylethinylmagnesium halide to the reactant. It is important to have the reactantand any liquid in which it may be dissolved free of water, alcohol, etc.audit is desirable to exclude atmospheric moisture and carbon dioxidefrom the reaction ssel with the aid of a soda-lime trap. The rate fadding the reactant should be regulated so that the reaction does notbecome We may also useas reactants certain types of v ethers exemplifiedby ethylene oxide and ethyl orthoformate. The nature of the action ofthe vinylethinyl magnesium halides'on these'- reactan'ts is' illustratedby the following equations:

so vigorous as to cause violent refluxing. After all the reactant hasbeen added itis usually advisable to heat the mixture so that it boilsgently for a short time (15 to 60 minutes) to insure completion of thereaction. 'Iheproductof the We may also use as reactants halides ofother elements than carbon including halides of mer- Cum, boron,silicon, germanium, tin, lead, phos- J-phorus, arsenic, antimony, andbismuth. The

I nature of the action of the vinylethinyl magnesium halide on thesehalides is illustrated by the following equations:

It is evident, therefore, that theprocess of the I present inventionmakes it possible to prepare a I great variety of new compounds. Thecompounds producedby the interaction of. the 'vinylethinyl magnesiumcompounds and a reactive agent in the manner described above, aresubstituted monovinylacetylenes in which a substituent group other than'hydrogenis attached to the alpha a vinylethinyl magnesium halidepreparedbyj the process described in the foregoing exam'pl'es. Re-

action usually occurs smoothlyand rapidly at the ordinary temperature oreven at temperatures L as low as ,10 C. In certain caseshowever, it

is necessary to heat the mixture to ashigh'a temperature as 120 C.' tocause the reaction to becompleted. A preferred method of bringing aboutthe mixing is toplace the solution of the vinylethinyl magnesium-halidein a vessel proreaction usually remains dissolved in the T3810 tionmixture. To isolate it, the solution is treated with ice-cold dilutemineral acid or ammonium chloride solution, the aqueous layer isremoved, .the organic layer is washed with water and dried,'and thesolvent is allowed to evaporate or distill. The. product thus isolatedcan usually be purified by distillation or crystallization.

7 The following examples illustrate the nature of our invention:

EXAMPLE III Preparation of a hydrocarbon containing the vinylethinylgroup A slight excess of vinylethinyl magnesium bromide is treated witha solution of lflgrams of triphenyl chloromethane in" anhydrous ether.=

After the completion of the reaction, the mixture is worked up bytreating with water and dilute acid, separating the ethereal layer, andallowing the ether to evaporate. This yields 75 grams, of a crystallinesolid, vinylethinyl triphenyl methane. 0.-

This. new compound melts at 134- .In a similar manner other compounds ofthe formula I in which R represents a hydrocarbon residue,

can be prepared by treating reactants consisting of alkyl halidescontaining very reactive halogen atoms} with vinylethinyl magnesiumhalide. Compounds of this classcan also be prepared by treating estersof sulfuric acid or aromatic sulfonic acids with vinylethinyl magnesiumhalides.

EXAMPLE IV Preparation of an amide containing the vinyl- 1 ethinyl groupA solution of 9 grams of alpha-naphthyl isocyanate in anhydrous ether isadded slowly to an excess of vinylethinyl magnesium bromide in ether.The mixture is refluxed for 30 minutes and then poured onto crushed ice.The ethereal solution is separated andallowed to evaporate.

. The crystalline residue is recrystallized from 50% alcohol. Theproduct thus obtained in 93% of the calculated amount is thenaphthylamide of vinylpropiolic acid melting at 125-126 C. This is anewcompound.

v magnesium bromide is cooled to 0 C. and shaken Other isocyanates maybe usedsimilarly to produce analogouscompounds.

EXAMPLE V I Preparation of vinylpropiolic acid One mol of an etherealsolution of vinylethinyl with carbon dioxide until a color test showsthe absence of any organo-magnesium halide. The solution is then treatedwith water and dilute acid. The ethereal layer is separated and theaqueous layer continuously extracted with ether Vinylethz'nyl carbinolsvinylethinyl cabinol, boilingat '59-81" C. at 17 mm. This is a newcompound.

grams of platinum-oxidecatalyst and shaken with i hydrogen at 2atmospheres for 45 minutes. I It absorbs 95% of the calculated amount ofhydrogen. Distillation of the liquid then givesv an excellent yield ofdimethyl n-butyl carbinol identical in its physical properties with thatalready described in the literature (Chem. Z. 1909, I, 1850.CHFCHCEC(IJ(CHz)z+BH- CH:CH:GH:GH:C(CH3):

OH H

In a manner precisely similar to that illustrated in Example VI a greatvariety of other vinylethinyl carbinols having the general formula in"which R and R are hydrogen, alkyl, or aryl,

can be obtained by treating aldehydes or ketones with vinylethinylmagnesium halides. The following table illustrates carbinols of thisclass that y can be obtained in this way. All of these are newcompounds.

Ketone or aldehyde reactant Formula 0! carbinol produced Physicalproperties of carbinol Acetaldeh de Acetophenone for 10 hours.Evaporation of the combined ethereal extracts yields 60 grams of a.liquid residue. When distilled at 2 mm. a considerable part of thismaterialdistills at 64-71" C. and the remainder is polymerized to aviscous rubber-like mass. The distillate is almost pure'vinylpropiolicacid, a' new compound. On being-heated it is ouFdii-c EpMgBr+C 0, H25 04Preparation of a mide in ethereal solution 40 g. of purified acetone isvadded slowly under a reflux condenser. After transformed into a toughrubber-like polymer.

a carbinol containing ethinyl group 1 .1 5 mols a vinylethinylmagnesium. proall the acetone has been added the reaction mix ture isgently heated for a. short time. It is then treated with water anddilute acid, the ethereal layer is separated, dried. and distilled.There is thus. obtained a 53% yield of pure dimeth'yl The vinylethinylcarbinols are colorless lisglids or crystalline solids having pleasantodors. e

are useful materials for the synthesis of a variety of compounds. Theycan be polymerized to clear, tough,' transparent resins. They arereadily hydrogenated to the corresponding saturated carbinols having thegeneral formula v ma mmmcmcmomcm Thus the hydrogenation of dimethylvinylethinyl carbinol as illustrated in Example VI yields .dimethyln-butyl carbinol. In a similar manner the hydrogenation of methyl ethylI vinylethinyl carbinolleads to methyl ethyl nthe-vinyl butyl carbinolagreeing in its properties with the compound of this structure alreadydescribed in the literature. Similarly the hydrogenation of methyln-octyl vinylethinyl carbinol yields methyl n-octyl n-butyl carbinol, acompound boiling at about 94 C. at 3 mm. and'having-a density of 20 C.,of 0.832; and the hydrogenation of methyl phenyl vinylethinyl' carbinolyields the compound methyl phenyl n-butyl carbinol, aliquid boiling at107-109 C. at 6 mm. and having i a density at20 C. of 0.962.

in which Y represents a halogen atom or a vinylethinyl group.

2. A proces of preparing a new composition of matter which comprisesreacting monovinyl acetylene with a Grignard reagent.

3. The process of preparing chemical compositions which comprisestreating a compound corresponding to the formula:

OH|=CH-CECMgY inwhich Y represents a halogen atom ora vinylethinylgroupwith-a 'Grignard reactive com-- pound containing atoms of twodiil'erent elements joined by more than one bond.

4. A product produced by the process of claim 3.

' 5. The process of preparing chemical compositions which comprisesreacting a compound corresponding to the formula:

CEFCH-CECMgY in which Y represents a halogen atom or a vinylethinylgroup with a compound containing atoms oi two diiferent elements joinedby more than one bond, said compound being of the group consisting ofaldehydes, -lzetones, nitrilea. carboxylic acid esters, carbon dioxide,isocyanates, isothiocyanates andsulfur dioxide. v

6. A product produced by the process of claim 5. 7. The processofpreparing chemical composions which comprises reacting a compoundcorresponding to the formula QHFOH-CECMgY in which Y represents ahalogen atom or a vinylethinyl group with an organic compound containinga carbonyl group.

8. The process of preparing chemical compositions which comprisesreacting responding to the formula CHFCH-CECMgY in which Y represents ahalogen atom or a vinyla compound corethinyl group withan organiccompound containing. a carbonyl group then hydrolyzing the resultingproduct.

9. The proces of preparing chemicalcompositions which comprises reactinga compound corto the formula capers-050mg 7 in which Y represents ahalogen atom or a, vinylethinyl group with an aldehyde.

10. The process of preparing chemical-compositions which comprisesreacting a'compound corresponding .to the formula v CH1'=CH-CECM;Y

in which Y represents a halogen atom or a vinylethinyl group with analdehyde then hydrolyzing the resulting product.

11. The process of preparing chemical compositions which comprisesreacting a compound corresponding to the formula in which Y represents ahalogen atom or a vinylethinyl group with a ketone.

12. The process of preparing chemical compositions which comprisesreacting a compound corresponding to the formula om=cH-cEcM Y in which Yrepresents a halogen atom or a vinylethinyl group with a ketone thenhydrolyzing the resulting product.

13. The process of preparing chemical compositions which comprisesreacting a compound corresponding to the formula cn onsezcm r in which Yrepresents a halogen atom' or a vinylethinyl group with acetone, thenhydrolyzing the resulting product.

14. The process of preparing chemical compositions which comprisesreacting a compound corresponding to the formula CHa=CH-CEQMgY v inwhich ,Y represents faihalogen atom or a vinylethinyl group withanorganic compound containing a carbonyl group, then hydrolyzing theresulting product and subsequently reacting with hydrogen.

15. The process of preparing chemical compositions which comprisesreacting a compound corresponding to the formula in which Y represents ahalogen atom or a vinylethinyl group with 'an aldehyde, then hydrolyzingthe resulting pr not and subsequently reacting with hydrogen. 1

' 16. The process of preparing compositions which comprises reacting acompound correo ding to the formula;

Cupolas-20mm in which Y- represents a halogen atom or .a vinylethinylgroup with a ketone, then hydrolyzing the resulting product and'subsequentLv reacting with hydrogen.

1'7. The process of preparing chemical compositionswhich comprisesreacting a compound corresponding to the formula CH|==CHCECMgY in whichY represents a halogen atom or a vinylethinyl group with an aldehyde;then hydrolyzing the resulting product and subsequently reacting withhydrogen in an amount suilicient to produce a saturated product.

18. The process of preparing chemical compositions which comprisesreacting a compound corresponding to the formula:

C HFCH-CEC MgY in which Y represents a. halogen atom or. a vinylethinylgroup with a ketone, then hydrolyzing the resulting product andsubsequently reacting with hydrogenin an amount sufiicient to produce asaturated product." 19. As new chemical compounds, carbinolscontaining-the vinylethinyl radical. p

20. As a new chemical compound dimethyl vinylethinyl carbinol.

21. The process which comprises reacting a vinylethinyl carbinol withhydrogen in the ence of a hydrogenating catalyst.

pres- 22. As new chemical compounds, amides of a vinylethinyl alphacarboiwlic acid.

23. .As new chemical alpha carboxyllc acids 24. New chemical compoundshaving the following formula OEv=0H-CECR.

1 compounds, vinylethinyl iao - monovinylacetylene with a Grignard'f'reagent monovinylacetylene with a Grignard mt then treating thereaction product with a Grignard. reactive compoimd containing atoms oftwo diiierent elements joined by more than one bond.

26. The process which comprises reacting monovinylacetylene with a.Grignard reagent then treating the reaction product with a compoundcontaining atoms of two difierent elements joined by more than one bond,said compound being of the group consisting of aldehydes, ketones,nitriles, carboxylic acid esters, carbon dioxide, isocyanates;isothiocyanates and sulfur dioxide.

27. The process which comprises reacting and treating the reactionproduct with an aidehyde.

28. The process which comprises reacting monovinylacetylene with aGrignard reagent and treating the reaction product with a ketone.

monovinylacetylene with a Grignard reagent, treating the reactionproduct with an aldehyde, then hydrolyzlng the resulting product andsubsequently reacting with hydrogen.

30. The process which comprises reacting monovinylacetylene with aGrigtnard reagent,

. treating the reaction product with a ketone, then hydrolyzing theresulting product and subsequentiyreacting with hydrogen.

31. Chemical compolmds having the following formula:

CHFCH-CEC-R in which R is a monovalent organic radical.

32. A polymer of a vinylethinyl alpha car- '29. The process .which'comprises reacting

